Disazo dyestuffs containing an n,n-dicyanoethyl group



United States Patent M Int. or. 0691) 31/04 US. Cl. 260186 2 ClaimsABSTRACT OF THE DISCLOSURE Disazo dyestuffs having one of the followingformulae C 112- C Hz- C N C Hz- 0 H2- 0 N Y X in which Y Y Y and Y eachrepresents a hydrogen or halogen atom or a methyl, methoxy or ethoxygroup and X represents a hydrogen or chlorine atom or a methyl ormethoxy group. These disazo dyestuffs are suitable for dyeing syntheticfibers and more especially polyesters and cellulose triacetate fibers.

The present invention relates to new disazo dyestuffs suitable fordyeing synthetic fibres, and more especially polyester and cellulosetriacetate fibres, in brilliant shades ranging from yellow to brownishred. In addition to an excellent fastness to light, these dyestuffs areexceptionally fast to sublimation. The problem of fastness to light isgenerally solved for polyester fibres by the use of dyestuffs of theanthraquinone series. However, this series is limited in the field ofyellow and orange shades.

The problem of sublimation assumes prime importance for the dyeing ofpolyester and cellulose triacetate fibers because of the hightemperatures to which these fibres are subjected. Especially during theheat-fixing, the sublimed dyestuff is liable to be deposited on the coldparts of the apparatus.

It has now been found according to the present invention that dyestuffsof the general formula:

CHzCHgCN i CH2CH2CN in which X represents a hydrogen or chlorine atom ora CH or OCH group, Ar represents a benzene or naphthalene nucleus andthe nuclei A and Ar may, if desired, be substituted by halogen atoms orCH OCH or O-C H groups, possess an excellent aflinity and enablefull-bodied yellow to red brown shades with very great fastness tolight, sublimation, over-dyeing, washing, seawater, perspiration,combustion gases, heat-fixing and folding to be obtained.

These dyestuffs may be synthesised, for example, by coupling anaminobenzene, which may be substituted, with the sulpho omega methylderivative (i.e. the sulpho group is at the end of the chain) of anotheraminobenzene or of an alpha aminonaphthalene, which may be Patented Nov.18,1969

substituted, saponifying the monoazo derivative obtained, diazotisingand coupling in acid medium, with or without neutralisation, with adicyanoethyl derivative of the formula:

in which X has the meaning given above.

As the first constituent there may be used, for example aniline, achloraniliue, a bromaniline, a toluidine, a anisidine, achlorotoluidine, a dichloraniline, or a xylidine; as theintermediateconstituent there may be used; for example, aniline, orthoormeta-toluidine, orthoor metaanisidine, meta-chloraniline, para-xylidine,the dimethyl or diethyl ethers of aminohydroquinone, 2,5-dimethylanilineor other similar bases; as the final constituent there may be used, forexample, dicyanoethylaniline, metatoluidine, meta-anisidine ormeta-chloraniline.

The dyeing'may be effected by known methods, for example, attemperatures below C. with a vehicle or above 100 C. under pressure. i

Compared with the disazo dyestuffs of'similar constitution which carryone or two hydroxyethyl groups, the dyestuffs according to the inventionare much faster to light.

By way of indication, the fastness of the dyestufi":

on polyester fibres, measured on the fadeometer, is 1 to 2. while thatof the dyestuff:

CHzCHzCN at the same depth of colour, is 5 to 6.

The dyestuif of the formula:

CHzCHzCN and its use for dyeing cellulose acetate have already beendescribed, but this dyestuff has only a very weak affinity for thisfibre and poor fastness to light. From this fact it could not beforeseen that the dyestuffs of the invention which have both anexcellent fastness to light and an excellent affinity and are very fastto sublimation, could be used on polyester fibres. Several patentsmention the use of dicyano ethyl derivatives of aniline and itshomologues, but in none of them is the preparation of disazo compoundsmentioned. The latter represent an advance on account of their betterfastness to sublimation.

The following examples illustrate but do not limit the invention.

EXAMPLE 1 19.8 parts of 4-amino-azobenzene are made into a paste in 40parts of 20 B. hydrochloric acid, diluted and diazotised for 2 hourswith a solution of sodium nitrite. On the other hand, 22 parts ofN,N-dicyanoethyl-meta-toluidine are dissolved in 50 parts of ethylalcohol and poured into the solution of the diazo compound. Afterstirring for several hours, the dyestuff obtained is filtered off andwashed. The paste is mixed with a dispersing agent, for example sodiumdinaphthylmethanedisulphonate, dried and ground. The dyestuff obtaineddyes polyester or cellulose triacetate fibres in shades of yelloworange.

The following table gives some other examples prepared the fibre anddoes not migrate to the cold parts of the m an analogous manner toExample 1. apparatus.

Example First constituent Intermediate constituent Final constituentShade Aniline Aniline N ,N-dicyanoethyl aniline Reddish-yellow. 34-chloro-2-methylaminobenzene Meta-anisidine o Yellow-orange.Ortho-broman1l1ne D o.

6 Meta chloran11me Meta-anisidine. 0.-

An ine Alpha naphthylammm ,N-dicyanoethyl-meta-toluidine Brownish-red8..- 2,4-d1chloroanil1ne Meta-anisidlne o Oran ge Brownish-red.

d n Aminohydroquinone dimethylether do 2,5 dich1oroan1line eta-toluldindo. Orange. n Meta-chloranllme do Yellow-orange.

Red-orange.

13.- 2,4-xyl1dme Meta-toluidme -do. 14 Ortho-toluidine Ortho-toluidinedo Orange-red. gntillineh .1 1 1\A/lniizlirltfff .l N ,bg-dicyanoethylmeta-anisidine gedprange. 1 -0 orani 1ne e 31-0 013 111G O I 17Meta-toluidine Meta-anisidine ..do Rei i fange. 1g gngkllmeifivn fflnaniline id," N,Ndicyanoethyl-meta-ehloraniline geddish-yellow.

1 0-0 oranl 1ne e arau s e O T811 e. 20 r Ortho-toluidineOrtho-toluidine do Ye1lo%v-orange.

EXAMPLE 21 We claim: A printing paste of the following composition is20 1. Disazo dyestuffs having one of the formulae: ared: U X P Parts I/OHCH2CN 4 Dyestufi of Example 15 1o -N=N@-N=N N Sodiumdinaphthylmethane-disulphonate 14 25 v CH1CH2CN Ethylene glycolmonoethyl ether 50 Y 2 Water 300 Aqueous solution of sodium chloratecontaining 300 CH CHgCN g. per litre @N: A-N=N N Starch tragacanththickener 600 30 CH CH2CH2CN This paste is applied on a grooved rollerto a fabric of 3 polyester fibres, previously desized at 45 C. byalkaline washing. The colour is fixed by steaming under pressure at130l40 C. The fabric is rinsed and treated in the hot with an alkalinereducing bath containing 1 to 2 g. per litre of a nonylphenol-ethyleneoxide condensate. The fabric is coloured a red-orange shade of excellentfastin which U and V each represent a hydrogen or chlorine atom, V isfixed on the position 4 or 5. X represents 5 a hydrogen atom or a methylor methoxy group, and Y and Z each represent a hydrogen or chlorine atomor a methyl or methoxy group.

2. Disazo dyestuifs according to claim 1 in which U and ness; thereserved parts being white. V are hydrogen atoms 40 EXAMPLE 22References Cited A foularding bath of the following composition is pre-UNITED STATES PATENTS pared Parts 2,821,526 1/1958 Boyd 260 20s Rh ner260205 Dyestuif of Example 6 30 2,941,992 6/1960 y Sodiumdinaphthylmethane-disulphonate 7 3092616 6/1963 Gaetam 260 186 Starchtragacanth thickener 5 CHARLES B. PARKER, Primary Examiner DONALD M.PAPUGA, Assistant Examiner Water 58 A strip of polyester fabric isfoularded several times in this dispersion and heat-fixed for one minuteat 200 C. U.S. Cl. X.R. Since the dyestuif is fast to sublimation, itremains on 841, 260-191 IN THE UNITED STATES PATENT OFFICE CERTIFICATEOF CORRECTION Patent No. 3, 479, 322 Dated Nov. 18, 1969 A. H. PetersonIt is certified that error appears in the above-identified patent andthat said Letters Patent are hereby corrected as shown below:

In the patent, Col. 3, line 36 "marco" should read macro Col. 4, line 2"monotrnor" should read -montmc Col. 4, line 35 "primer" should read--trimer-- SIGNED fiND SEALED JUN 2 gm (SEAL WIN-1AM E. $080M I Edn 1 mmIn Comissioner of la'bntl

